WO2019095245A1 - Procédé de synthèse d'un composé disulfonate de méthylène - Google Patents

Procédé de synthèse d'un composé disulfonate de méthylène Download PDF

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Publication number
WO2019095245A1
WO2019095245A1 PCT/CN2017/111504 CN2017111504W WO2019095245A1 WO 2019095245 A1 WO2019095245 A1 WO 2019095245A1 CN 2017111504 W CN2017111504 W CN 2017111504W WO 2019095245 A1 WO2019095245 A1 WO 2019095245A1
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WO
WIPO (PCT)
Prior art keywords
methylene disulfonate
synthesizing
acid
disulfonate compound
compound
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PCT/CN2017/111504
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English (en)
Chinese (zh)
Inventor
张民
刘鹏
王军
Original Assignee
石家庄圣泰化工有限公司
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Application filed by 石家庄圣泰化工有限公司 filed Critical 石家庄圣泰化工有限公司
Priority to KR1020187023253A priority Critical patent/KR102101982B1/ko
Priority to PCT/CN2017/111504 priority patent/WO2019095245A1/fr
Publication of WO2019095245A1 publication Critical patent/WO2019095245A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms

Definitions

  • the invention belongs to the technical field of battery electrolyte additives, and relates to a battery electrolyte additive, a methylene disulfonate compound, and particularly relates to a method for synthesizing a methylene disulfonate compound.
  • the synthesis method of the invention is simple, the yield is high, the obtained product has high purity, low moisture content and low acid value, and the application to the battery electrolyte can greatly improve the performance of the electrolyte.
  • the methylene disulfonate compound can be used as a pharmaceutical preparation for treating leukemia and the like in animals, and the sulfonic acid group contained in the structure can react with alcohol, phenol, thiol and the like under certain conditions, and its unique structure. It has a huge role in the synthesis of heterocyclic drugs.
  • the application of methylene disulfonate compounds in lithium battery electrolyte additives has been gradually developed.
  • the methylene disulfonate compound is used in lithium battery electrolyte additives, which can be remarkable. Improve battery performance, increase battery rechargeability and cycle characteristics.
  • the moisture content and acid value of the methylene disulfonate compound prepared by the prior method are relatively high, and are applied to the battery to cause decomposition, flatulence and bulging of the electrolyte, which not only fails to improve the performance of the battery, but also significantly The performance of the battery is lowered, and therefore, the moisture content and acid value of the added additive must be strictly controlled.
  • a sulfonyl chloride is reacted with silver carbonate to obtain silver sulfonate, and then silver sulfonate is reacted with diiodomethane, and R is a hydrogen atom or a methyl group:
  • the raw material diacetate used in this production method is very expensive and not easily available, and the alkane disulfonic acid which is additionally used as a raw material is also expensive to affect its industrial application.
  • This method reduces the production cost to a certain extent, but the yield is low and can only reach about 50%. Moreover, the obtained product has high moisture content and high acid value, affecting the performance applied to the battery, and has no industrial value.
  • the present invention provides a method for synthesizing a methylene disulfonate compound, which has a mild and stable synthesis process, and greatly improves the yield and product quality.
  • the structural formula of the methylene disulfonate compound of the present invention is as shown in the following II: R 1 and R 2 are independently a hydrogen atom or a C 1-4 alkyl group in which a hydrogen atom may be substituted by a halogen atom; n is 1 to 4 An integer; and when n is an integer from 2 to 4, n R 1 and n R 2 may be the same or different;
  • a method for synthesizing a methylene disulfonate compound which is synthesized by reacting an alkanedisulfonic acid with a formaldehyde compound in the presence of a dehydrating agent, wherein the dehydrating agent is a neutral dehydrating agent, and the alkane disulfonic acid is used.
  • the sulfonic acid compound of the formula I controlling the molar ratio of the formaldehyde compound to the alkanedisulfonic acid ⁇ 1; wherein R 1 and R 2 are independently a hydrogen atom or a C 1-4 alkane which may be substituted by a halogen atom n is an integer from 1 to 4; and when n is an integer from 2 to 4, n R 1 and n R 2 may be the same or different;
  • the molar ratio of the formaldehyde compound to the alkanedisulfonic acid is (1 - 1.3): 1.
  • Formaldehyde compound Do not use too much, otherwise it will increase the moisture content of the final product, so the molar ratio to the alkanedisulfonic acid should be controlled to be (1-1.3):1.
  • the reaction temperature was controlled to be less than 100 ° C, and the atmospheric pressure reaction time was 1-2 h.
  • the reaction temperature is controlled to be less than 100 ° C in order to better remove moisture, and to prevent the partial contact of the methylene disulfonate compound caused by condensation after evaporation of water to entrap moisture into the crystal, resulting in an increase in the moisture content of the product.
  • the three-stage temperature control method is adopted in the reaction process.
  • the temperature in the first stage is the lowest, the temperature in the third stage is second, and the temperature in the second stage is the highest. Specifically: the temperature is controlled at 20-30 ° C for 15-20 min, then the temperature is controlled at 50-90 ° C for 30-50 min, then the temperature is controlled at 30-50 ° C for 20-25 min, but the temperature of the third stage is higher than the first The height of one stage is lower than that of the second stage.
  • the low temperature reaction at 20-30 °C is to make the reaction process mild, avoiding the reaction being too intense at high temperature, causing by-product formation and water doping, which acts as a buffer; then controlling the high temperature reaction at 50-90 °C is In order to promote the reaction, the conversion rate is accelerated; finally, at a low temperature of 30-50 ° C, it is a slowing process of the reaction, allowing it to stabilize the continuous reaction, while the final stage of cooling can prevent the cooling time from being long and the temperature difference is large after the reaction is completed.
  • the crystal encapsulates moisture defects. Three-stage temperature control can greatly shorten the response
  • the molar ratio of the dehydrating agent to the alkanedisulfonic acid is (1-1.3):1.
  • the neutral dehydrating agent is selected from one or a combination of anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium sulfate, molecular sieves, and silica gel.
  • the formaldehyde compound is selected from the group consisting of paraformaldehyde, anhydrous formaldehyde, and three One or several combinations of alkane.
  • the mixture containing the methylene disulfonate compound is separated by adding an extractant thereto for extraction, and then the extract is subjected to decolorization, suction filtration, concentration, crystallization, and drying to obtain a methylene disulfonate compound.
  • the extracting agent is a mixture of one or more of dichloromethane, chloroform, carbon tetrachloride, ethyl acetate, methyl acetate and isopropyl acetate, and the mass ratio of the extracting agent to the alkanedisulfonic acid is (4-10): 1.
  • the amount of extractant is the key to achieve the extraction effect. Too little will make the extraction incomplete, resulting in low yield; too much will increase the difficulty and time of subsequent extraction agent, and will also cause partial hydrolysis, affecting the yield and quality of the product. .
  • the crystallization is carried out by continuous cooling, and is kept at -10 to -15 ° C for 10-15 minutes, and then cooled to -30 to -40 ° C at a rate of 1-2 ° C / min to complete crystallization.
  • the control of the crystallization mode and conditions of the present invention is to prevent entrapment of water during the crystallization process, resulting in an increase in moisture content and affecting the properties and properties of the product.
  • the method for producing the methylene disulfonate compound has the advantages of low cost and remarkable economic benefit; the reaction process is mild and stable; the alkanedisulfonic acid can be solid or liquid, and the reactant can be directly reacted or in the solvent.
  • the reaction is carried out in a simple and easy process.
  • the advantage of the reaction yield of the alkanedisulfonic acid and the formaldehyde compound is more than 75%, and the yield is improved by more than 25% compared with the prior art, and a qualitative leap is achieved.
  • the acid value and moisture content are also greatly reduced, and this effect causes the flatulence and bulging of the battery to be lowered.
  • the invention particularly emphasizes the use of a neutral dehydrating agent, which is to promote the reaction and increase the conversion rate on the one hand, and to combine with water if an acidic dehydrating agent such as phosphorus pentoxide is used in our research.
  • an acidic dehydrating agent such as phosphorus pentoxide
  • the important reason that the low can only reach about 50% (such as the patent document with the application number of 200780014629.X), the micro-environment is easily overlooked, and the seemingly insignificant influence is very large.
  • the present invention particularly emphasizes that the molar ratio of the formaldehyde compound to the alkanedisulfonic acid is ⁇ 1, and the amount of the formaldehyde must be excessive.
  • the purpose is not to complete the reaction of the alkanedisulfonic acid, but to create a disulfonic acid.
  • the stable presence of the methyl ester compound avoids the problem of yield reduction due to hydrolysis of the methylene disulfonate compound and avoids an increase in the acid value. If the amount of the alkanedisulfonic acid is excessive, the above effect cannot be achieved.
  • the nuclear magnetic spectrum is 1 H-NMR (400 MHz, CD3CN) ⁇ (ppm): 5.72 (s, 2H), 2.33 (s, 4H), 1.33 (s, 4H) 0.90 (s, 6H).
  • the moisture content was measured to be 15 ppm and the acid value was 17 ppm.
  • Example 2 Compared with Example 1, an acidic catalyst such as phosphorus pentoxide was used, and the other conditions were the same, and 996.4 g of a product was obtained, the calculated yield was 53%, the detected moisture content was 58 ppm, and the acid value was 70 ppm.
  • an acidic catalyst such as phosphorus pentoxide was used, and the other conditions were the same, and 996.4 g of a product was obtained, the calculated yield was 53%, the detected moisture content was 58 ppm, and the acid value was 70 ppm.
  • Example 2 Compared with Example 1, 1760 g (10 mol) of methanedisulfonic acid and 261 g (8 mol) of 92% paraformaldehyde were added, and the other conditions were the same, 821.2 g of the product was obtained, the calculated yield was 54.6%, and the detected moisture content was 60 ppm. The acid value is 80 ppm.
  • the obtained filtrate was concentrated to obtain crystals, and the obtained crystals were dried at 40 ° C and 10 mmHg for 6 hours to obtain 4.7 g of methylene methanesulfonate methane as a pale brown crystal.
  • the yield was 50%, the detected moisture content was 65 ppm, and the acid value was 86 ppm. .
  • the obtained filtrate was concentrated to obtain crystals, and the obtained crystals were dried at 40 ° C and 10 mmHg for 6 hours to obtain 7.0 g of light brown crystals of methylene chloride of 1,2-ethanedisulfonate, the calculated yield was 69.2%, and the detected moisture content was 73 ppm. , acid value of 90ppm.
  • the development and application of battery additives is to improve and improve the performance of the battery.
  • the acid value and moisture content of the additive affect the performance of the battery, which also affects the life of the electrolyte. If the acid value and moisture content are high, it is easy to cause acid hydrolysis and deterioration. The gas is scrapped and affects the high and low temperature stability of the battery.
  • the methylene disulfonate compound prepared above is added as an additive to the same electrolyte in the same amount, and the performance of the battery is tested for comparison and verification.
  • the diaphragm is made of ceramic diaphragm to form a soft pack battery. After injecting the electrolyte, it is assembled into a soft pack battery in the glove box, and it is tested after standing for 8 hours. The application performance was tested and the results were as follows.
  • the battery was activated by charging and discharging at a temperature of 25 ° C at a constant temperature of 25 ° C, respectively, and then charged and discharged at 1 °C under a cycle of 45 ° C.
  • the cycle test results are shown in Table 1.
  • Battery discharge retention rate at different rates discharge the battery to 3.0V with a constant current of 0.5C, and put it on hold 5min, then charged to a voltage of 4.5V or more with a constant current of 0.5C, and charged at a constant voltage, the current is 0.05C, left for 5min, and then discharged at a constant current of 0.2C, 1C, 1.5C, 2C to a voltage of 3.0V.
  • battery high-temperature storage performance evaluation 60 ° C / 30D and 85 ° C / 7D storage performance test, the following list 3 is the battery after the standard charge and discharge, then stored at 60 ° C for 30 days and 85 ° C for 7 days, then measure the battery capacity retention Rate and capacity recovery rate.
  • Table 4 battery low-temperature storage performance evaluation; Table 4 is to put the battery in the low temperature box, separately controlled The temperature was -30 ° C or -40 ° C, the hold time was 240 min, and then the capacity retention of the battery was measured.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne un procédé de synthèse d'un composé disulfonate de méthylène, qui se rapporte au domaine technique des additifs d'électrolyte de batterie. Le composé disulfonate de méthylène est synthétisé par réaction d'un acide alcanedisulfonique avec un composé formaldéhyde en présence d'un agent déshydratant. L'agent déshydratant est un agent déshydratant neutre. L'acide alcanedisulfonique est un composé d'acide sulfonique représenté par la formule I, le rapport molaire du composé de formaldéhyde à l'acide alcanedisulfonique est ≥ 1, dans la formule R1 et R2 représentent indépendamment un atome d'hydrogène, un alkyle en C1-C4 éventuellement substitué par un atome d'halogène, n est un nombre entier de 1 à 4, et lorsque n est un nombre entier de 2 à 4, n cas de R1 et n cas de R2 peuvent être identiques ou différentes. Le procédé de synthèse selon la présente invention est simple, et présente un rendement élevé. Le produit présente une pureté élevée, une faible teneur en humidité et une faible valeur d'acide. Le produit selon l'invention peut augmenter de manière considérable la performance d'un électrolyte de batterie.
PCT/CN2017/111504 2017-11-17 2017-11-17 Procédé de synthèse d'un composé disulfonate de méthylène WO2019095245A1 (fr)

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KR1020187023253A KR102101982B1 (ko) 2017-11-17 2017-11-17 메탄디설포네이트 화합물의 합성 방법
PCT/CN2017/111504 WO2019095245A1 (fr) 2017-11-17 2017-11-17 Procédé de synthèse d'un composé disulfonate de méthylène

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN111072626A (zh) * 2019-12-24 2020-04-28 湖南阿斯达新材料有限公司 一种环状二磺酸亚甲酯化合物的制备方法
CN115872972A (zh) * 2022-12-30 2023-03-31 无锡零一未来新材料技术研究院有限公司 一种甲基二磺酸亚甲酯的制备方法

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CN101426776A (zh) * 2006-04-26 2009-05-06 住友精化株式会社 制备二磺酸亚甲酯化合物的方法
CN107098882A (zh) * 2017-04-17 2017-08-29 长园华盛(泰兴)锂电材料有限公司 一种甲烷二磺酸亚甲酯的合成方法

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KR100696632B1 (ko) 2005-07-29 2007-03-19 삼성에스디아이 주식회사 표시장치용 다층 기재 및 이를 구비한 표시장치
TWI508956B (zh) * 2010-08-25 2015-11-21 Sumitomo Seika Chemicals Preparation method of methylene disulfonate compound
JP5724366B2 (ja) * 2010-12-21 2015-05-27 セントラル硝子株式会社 環状ジスルホン酸エステル化合物の製造方法
CN106916138B (zh) * 2017-03-01 2019-04-09 山东永浩新材料科技有限公司 一种甲烷二磺酸亚甲酯的合成方法

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CN101426776A (zh) * 2006-04-26 2009-05-06 住友精化株式会社 制备二磺酸亚甲酯化合物的方法
CN107098882A (zh) * 2017-04-17 2017-08-29 长园华盛(泰兴)锂电材料有限公司 一种甲烷二磺酸亚甲酯的合成方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111072626A (zh) * 2019-12-24 2020-04-28 湖南阿斯达新材料有限公司 一种环状二磺酸亚甲酯化合物的制备方法
CN111072626B (zh) * 2019-12-24 2022-11-15 湖南阿斯达新材料有限公司 一种环状二磺酸亚甲酯化合物的制备方法
CN115872972A (zh) * 2022-12-30 2023-03-31 无锡零一未来新材料技术研究院有限公司 一种甲基二磺酸亚甲酯的制备方法
CN115872972B (zh) * 2022-12-30 2024-01-19 无锡零一未来新材料技术研究院有限公司 一种甲基二磺酸亚甲酯的制备方法

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KR102101982B1 (ko) 2020-04-17

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